Preparation of indanyl-sulfides, sulfoxides and sulfones



United States Patent PREPARATION OF INDANYL-SULFIDES, SULFOXIDES ANDSULFONES Alexis A. Oswald, Sarnia, Ontario, Canada, assignor to EssoResearch and Engineering Company, a corporation of Delaware No Drawing.Filed Dec. 3, 1958, Ser. No. 777,861

7 Claims. (Cl. 260-607) This invention relates to the manufacture of newsubstances having properties that make them valuable as additives forlubricating oil compositions; modifiers for synthetic rubber andpetroleum resins; surface active agents; constituents of fly-repellants,insecticides, miticides, ovicides and fungicides; as intermediates foragricultural and pharmaceutical chemicals; and for other and numeroususes.

This invention has, as an object, the preparation of new and usefulchemical compounds. These new compounds may be represented by theformula:

RS-R' ))o1 wherein R is selected from the group consisting of theZ-indanyl radical and alkyl substituted 2-indanyl radicals wherein atleast one hydrogen atom on an indanyl radical is replaced by an alkylradical of l to 5 carbon atoms, and R is selected from the groupconsisting of a C to C aromatic hydrocarbon radical selected from thegroup consisting of phenyl, tolyl, xylyl, naphthyl and anthracylradicals, and a halogen substituted C6 to C aromatic hydrocarbon radicalwherein at least one hydrogen atom attached to an aromatic ring isreplaced by a halogen atom. A further object resides in devising novelprocedures whereby these new chemical compounds may be obtained. Otherobjects will appear hereinafter.

These objects are accomplished by a non-catalytic addition of mercaptansto indene and alkyl substituted indene compounds wherein one or morehydrogen atoms of the indene molecule are replaced by an alkyl radicalof l to 5 carbon atoms to produce indanyl sulfides and by the oxidationof these sulfides to the corresponding indanyl sulfoxides and sulfones.

. The addition of mercaptans to olefins in general is a known reactionusually proceeding concurrently with both an ionic and a radical chainmechanism. It is generally necessary to use a catalyst which initiatesmercapto radicals for effecting a mercaptan addition predominantly witha radical mechanism. However, it was 2,968,678 Patented Jan. 17, 1961.sures in the range of 0.2 to 50 atmospheres. The reactions may becarried out either with or without the employment of an inert diluentsuch as methanol, benzene, chloroform and n-hexane.

The sulfoxides of this invention are prepared by the oxidation ofindanyl sulfides at a temperature in the range of -20 C. to 100 C. Theoxidant for these reactions may be air, molecular oxygen, ozone,hydrogen peroxide or peracids.

The sulfones of this reaction are prepared by a more vigorous oxidationof indanyl sulfides than is employed in the production of the aforesaidsulfoxides. In addition for the preparation of the sulfones, a doublequantity of the oxidant is necessary than that which is used for thepreparation of sulfoxides. Indanyl sulfones are prepared at temperaturesin the range of -20 C. to 150 C. Suitable oxidants for preparing indanylsulfones include hydrogen peroxide, hydrocarbon hydroperoxides, peracidsand peracid salts. The oxidations are preferably carried out in anorganic solvent such as acetic acid or acetic anhydride or a mixture ofthe same.

The sulfide compounds herein involved may be prepared employingequimolar amounts of the mercaptan and indene reactants or either ofsuch reactants may be in excess. However, it is preferred that there beem- I ployed atleast one mole of the indene reactant per eachPreparation 0 indanyl phenyi sulfide 11.0 grams (0.1 mol) of thiophenoland 11.6 grams (0.1 mol) of indene were mixed in a reaction zone, i.e. a50 mls. round bottomed flask, and the mixture was kept around 90 C. fortwo hours. An exothermic reaction took place and the raw product (aliquid at this temperature) was obtained. The product was purified byvacuum distillation and 19.5 grams, i.e. a yield of 86% of indanylphenyl sulfide was obtained at between 145 and 146 C. at 2 mm. pressure.This product solidified at room temperature. Analysis of the productrevealed the following:

discovered in the present invention that mercaptans add with asurprising ease to indene and alkyl substituted indene compounds by aradical mechanism in the absence of catalysts. The mechanism of thereaction was proven by the identity of the sulfides from reactions inthe absence and in the presence of peroxides.

Mercaptans suitable for use with this invention include aromaticmercaptans and halogen substituted aromatic mercaptans such asthiophenol, toluene thiol,

EXAMPLE 2 Preparation of indanyl 4-t0luyl sulfide 12.4 grams (0.1 mol)of p-toluene thiol was dissolved in 11.6 grams (0.1 mol) of indene atroom temperature. The reaction mixture so obtained was allowed to standfor four days. By the end of this period it solidified to a crystalmass. This was recrystallized from n-heptane and ethanol to give 21.6grams, i.e. a yield of purified indanyl p-toluyl sulfide as white,rhombic plates. An analysis of the crystals revealed the following:

4 hydroperoxide were dissolved in a solvent mixture consisting of 150mls. of cyclohexane and 50 mls. of ben- Carbon Formula M.P. C.

Hydrogen Sulphur Calcd. Found Calcd. Found Calcd. Found -s-om 86-86. 580.0 80. 7

EXAMPLE 3 Preparation of indanyl 4-clzl0r0phenyl sulfide 14.5 grams (0.1mol) of 4-chlorothiophenol and 11.6 grams (0.1 mol) of indene and mls.of n-heptane solvent were mixed in a 100 mls. round bottomed flask. Theresulting solution was heated for 3 hours on a water bath. Then it wasallowed to come to room temperature, when the reaction productcrystallized out of the solution. After recrystallization from n-heptane23.2 grams, i.e. a yield of 89% indanyl 4-chlorophenyl sulfide wasobtained. An analysis revealed the following:

zene. The resulting solution was allowed to stand for 12 hours at roomtemperature in a 300 mls. bottle closed air-tight. The bottle was openedand heated on a water bath at 78 C. for one-half hour while bubblingnitrogen into the solution (blanket against oxidation). Then thesolution was allowed to cool to room temperature, while continuingnitrogen bubbling for concentration. The concentrate was recrystallizedfrom benzenecyclohexane and gave 22.7 grams, i.e. a yield of 87% indanyl4-chlorophenyl sulfide. The substance had a melting point of 89-905 C.and gave no melting point Carbon Formula M.P. 0.

Hydrogen Sulphur Oaled. Found Calcd. Found Calcd. Found EXAMPLE 4Preparation of indanyl Z-naphthyl sulfide 8 grams (0.05 mol) ofZ-naphthalene thiol was dissolved in 5.8 grams (0.05 mol) of indene byheating on a water bath. After the dissolution of the 2-naphthalenethiol, the reaction mixture was allowed to cool down and stand for 4days at ambient temperature. The crystal mass resulted after this periodwas recrystallized from 30 rule. of n-heptane and yielded 12.6

grams, i.e. 91% purified indanyl naphthyl sulfide as needle-likecolourless crystals. An analysis of the product revealed the followingcomposition:

depression with the product prepared with the method described inExample 3.

EXAMPLE 6 Preparation of indanyl 4-t0luyl sulfoxide 2.4 grams (0.01 mol)of indanyl p-toluyl sulfide were dissolved in a mixture of 40 mls.acetic anhydride and 15 mls. of acetic acid. To the solution 0.01 mol(0.34 gram) of hydrogen peroxide was added in the form of an aqueous 30%solution. The reaction mixture was allowed to stand for three days atroom temperature. The solution was then diluted with 3 volumes of waterand the raw sulfoxide precipitated. The raw Preparation 0;! indanyl4-chl0r0phenyl sulfide in the presence 0] cumene hydroperoxide catalyst14.5 grams (0.1 m'ol) 4-chlorothiophenol, 11.6 grams product wasrecrystallized from methanol, and 2.3 grams,

i.e. a yield of 79%, of indanyl 4-toluyl sulfoxide was ob tained. Thiscompound is a white crystalline substance at room temperature. Ananalysis of this compound (0.1 mol) indene and 0.75 gram (0.005 mol).cumene. revealed. the following:

Carbon Hydrogen Sulphur Formula M.P. C.

Calcd. Found Calcd. Found Calcd. Found S -cm 107-108 75.00 74.89 8.256.34 12.5 r 12.8

EXAMPLE 7 EXAMPLE 9 Preparation of indanyl 4-chlorophenyl.sulfoxide 13grams 0.05 mol) indanyl 4-chlorophenyl sulfide was dissolved in aceticanhydride-acetic acid mixture and reacted with an aqueous solution of0.05 mol 1.7 grams) of hydrogen peroxide under conditions given in thepre Preparation of indanyl 4-toluyl sulfone 2.4 grams (0.01 mol) ofindanyl p-toluyl sulfide was dissolved in a mixture of mls. of aceticanhydride and 15 mls. of acetic acid. To this solution 0.2 mol (0.68gram) hydrogen peroxide was added and the so lution was heated on awater bath for fifteen minutes. The reaction mixture was then dilutedwith 3 volumes of water to precipitate the crude product. This was thenrecrystallized from methanol. A yield of 2.6 grams,

Carbon Hydrogen Sulphur Formula Ml. C.

. Calcd. Found Calcd. Found Calcd. Found @fi-Q-m 97-98 65.08 84.84 4.734.83 11.58 106 EXAMPLE 8 Preparation of indanyl 4-toluyl sulfoxide fromp-toluene thiol and indene in one step 6.2 grams (0.05 mol) of p-toluenethiol, 5.8 grams i.e. a yield of 94% of indanyl 4toluyl sulfone wasobtained. This product is a white crystalline solid at room temperature.An analysis of this product revealed the following:

Carbon Hydrogen Sulphur Formula M.P. C.

Calcd. Found Calcd. Found Calcd. Found i -1CH1 134.5-135.5 70.59 70416.88 591 11.76 11.3

(0.05 mol) of indene and a mixture containing 9 grams (0.1 mol) butylhydroperoxide and 3.7 grams (0.025 mol) bis-tertiary-butyl peroxide wereplaced into 2150 mls. round bottomed flask. The reaction mixture so0btained was heated on awater bath untila strong evolution of bubblesindicated decomposition (2-3 minutes at water bath temperature). Then itwas cooled to room temperature and allowed to stand for 3 days. Afterthis period the volatile byproducts were removed by distil-j lation froma water bath at 10 mm. pressure. Theiresidue was filtered and the solidremained on the filter'was recrystallized from benzene-n-heptane. 8grams, i.e. a yield of 62.4% indanyl 4-toluyl sulfoxide was obtained.This product did not give melting point depression in mixture with thesubstance prepared in Example 6.

EXAMPLE 10 Preparation of indanyl phenyl sulfone 11.3 grams (0.05 mol)of-indanyl phenyl sulfidewas dissolved in a mixture of 35 mls. aceticanhydride and 15 mls. acetic acid. The solution was warmed up to 60 C;and 0.1 mol (3.4 grams) of hydrogen peroxide was added dropwise to it inthe form of an aqueous 30% solution while keeping it at thistemperature. Thereafter the solution was heated to C. in the course of15 minutes. Then it was allowed to come to room temperature and mixedwith a triple quantity of ice for the precipitation of the sulfone.After recrystallization' from methanol 12.6 grams, Le. a yield of 91%white crystalline product was obtained. An analysis revealed thefollowing:

1 Carbon Hydrogen Sulphur Formula M.P. C.

Caled. Found Calcd. Found Cnlcd. Found 7 EXAMPLE 11 Preparation ofindanyl 4-ehlor0phenyl sulfone 13.9 grams (0.05 mol) of indanyl4-chlorophenyl sulfoxide is dissolved in a mixture of 30 mls. aceticacid and 60 mls. acetic anhydride. To the solution 0.05 mol (1.7 grams)of hydrogen peroxide is added in the form of an aqueous 30% solution.The reaction mixture is kept for three days at room temperature. Thesolution is then diluted with 4 volumes of water and the raw sulfoneprecipitated. The raw product is recrystallized from ethanol and 13.8grams, i.e. 94% of indanyl 4-chlorophenyl sulfone is obtained. Ananalysis of the white crystalline product revealed the following:

8 What is claimed is: V 1. A composition of matter represented by theformula R--fiR ()0-1 wherein R is selected from the group consisting ofthe 2-indanyl radical and alkyl substituted 2-indanyl radicals whereinat least one hydrogen atom of the 2-indanyl radical is replaced by a Cto C alkyl radical and R is a C to C aromatic radical selected from thegroup consisting of phenyl, tolyl, xylyl, naphthyl and anthracylhydrocarbon radicals and monochlorinated derivatives there- CarbonHydrogen Sulphur Formula Calcd. Found Caled. Found Calcd. Found it s o161.53 61.73 4.47 4.75 10.95 10.1

EXAMPLE 12 Preparation of indanyl Z-naphthyl sulfon-e of wherein ahydrogen atom is replaced by a chlorine atom.

. 2-indanyl 4-toluyl sulfide.

2-indanyl 4-chlorophenyl sulfide.

. 2-indanyl Z-naphthyl sulfide.

Z-indanyl 4-chlorophenyl sulfoxide.

Z-indanyl 4-chlorophenyl sulfone. A noncatalytic process for preparing acomposition of matter represented by the formula wherein R is selectedfrom the group consisting of the 2-indanyl radical and alkyl substituted2-indanyl radicals 0 wherein at least one hydrogen atom of the Z-indanylradi- Carbon Hydrogen Sulphur Formula M.P. C.

Calcd. Found Oalcd. Found Calcd. Found i H 140-141 73.99 74.08' 5.236.18 10.4 9.7 0 I EXAMPLE 13 cal is replaced by a C to C alkyl radicaland R is a The preparation of n miticide composition using indanyl4-chlorophenyl sulfane 10 grams of indanyl 4-chlorophenyl sulfone and 90grams of talcum po-wder are added into a small ball mill. Then thecontents are milled for 2 /2 hours in order to obtain a thorough mixingof biologically ac tive indanyl 4-chloropheny1 sulfone and the talcumcarryingagent. By this method a free flowing powder is obtained. Thiscan be applied by conventional dusting machinery on agricultural crops,e.g. cotton infested with arachnids (order Acarina). hours theinfestation is found to be markedly reduced.

It is to be understood that all percentages recited herein unlessotherwise designated refer to weight percents.

The term Z-i'ndanyl radical is used herein to refer to the residue of anindane molecule from which a hydrogen atom has been removed from thenumber 2 carbon atom.

Upon inspection after 24 C to C aromatic hydrocarbon radical selectedfrom the group consisting of phenyl, tolyl, xylyl, 'naphthyl andanthracyl hydrocarbon radicals and monochlorinated derivatives thereofwherein a hydrogen atom is replaced by a chlorine atom which comprisesreacting a mercaptan represented by the formula References Cited in thefile of this patent Champaigne et al.: J. Am. Chem. Soc., 76, 1272-5(1954).

1. A COMPOSITION OF MATTER REPRESENTED BY THE FORMULA
 7. A NONCATALYTIC PROCESS FOR PREPARING A COMPOSITION OF MATTER REPRESENTED BY THE FORMULA 